JP6469605B2 - Gas barrier film - Google Patents

Description

  The present invention relates to a gas barrier film having an organic layer and an inorganic layer, and relates to a gas barrier film excellent in adhesion between a support and an organic layer.

Gas barrier films that block moisture and oxygen are used for the purpose of protecting various members and materials.
For example, in recent years, in a display device using an organic electroluminescence element (organic EL element) or plastic liquid crystal, these are sealed with a gas barrier film in order to protect the organic EL element or plastic liquid crystal.
Moreover, in a solar cell, since the photovoltaic cell which has a photoelectric converting layer etc. is weak to a water | moisture content, sealing a photovoltaic cell with a gas barrier film is performed.

The gas barrier film usually has a structure in which a gas barrier layer that expresses gas barrier properties is formed on the surface of a resin film or the like as a support.
In addition, as a structure that exhibits high gas barrier properties, an organic / inorganic laminate type gas barrier having at least one combination of an inorganic layer and an organic layer serving as an underlayer of the inorganic layer on the support as a gas barrier layer. Film is known.
The organic / inorganic laminated gas barrier film forms an inorganic layer exhibiting gas barrier properties on an organic layer serving as a base. As a result, the surface where the inorganic compound that forms the inorganic layer is difficult to deposit, such as unevenness and the shadow of foreign matter, on the surface on which the inorganic layer is formed, and an appropriate inorganic layer is formed on the entire surface of the substrate without any gaps. It becomes possible to do. As a result, the organic / inorganic laminated gas barrier film exhibits high gas barrier properties.

  As shown in Patent Document 1, in order to obtain high gas barrier properties in an organic / inorganic laminated gas barrier film, it is important to cover the entire surface with an inorganic layer without causing defects in the inorganic layer. For that purpose, it is important to appropriately cover the entire formation surface of the inorganic layer with an organic layer having a high glass transition temperature (Tg). In consideration of this point, in the organic-inorganic laminated gas barrier film, a (meth) acrylic polymer or the like is suitably used for the underlying organic layer serving as the inorganic layer.

By the way, in a structure using the organic EL element as described above or a configuration in which light is irradiated or incident from the gas barrier film side like a solar cell, the gas barrier film is required to have good optical characteristics such as high transparency. The
Therefore, as described in Patent Document 2, in a gas barrier film used for such applications, a retardation value such as a resin film made of cycloolefin polymer (COP) or cycloolefin copolymer (COC) is used as a support. It is preferable to use a support having a low (Re value).

  However, since the COP film and the COC film have low polarity, the adhesion with the (meth) acrylic polymer is very poor.

  Since the inorganic layer is formed on the surface of the support such as the COP film and then a combination of the base organic layer and the inorganic layer is formed on the inorganic layer as in Patent Document 2, the lower layer has the inorganic layer. The adhesion of the organic layer can be ensured by using a silane coupling agent or the like.

Here, the inorganic layer is formed by a vapor deposition method such as plasma CVD or sputtering. In addition, the higher the plasma intensity, the higher the density of the inorganic layer with high gas barrier properties.
In the configuration of Patent Document 1, the inorganic layer is formed directly on the surface of the support.
However, although the glass transition temperature of COP is high to some extent, the glass transition temperature and the melting point coincide. Therefore, depending on the glass transition temperature of the support, the support is deformed by the heat of the plasma when forming the inorganic layer. This deformation changes the retardation value of the support. In particular, the thickness direction retardation (Rth) varies greatly.
Therefore, depending on the glass transition temperature of the support, even if a support having a low retardation value such as a COP film is used, the intended optical characteristics may not be obtained.

On the other hand, Patent Document 3 describes that the organic layer is formed of a polymerizable compound containing a condensed polycyclic hydrocarbon structure. As an example, it is exemplified that the organic layer is formed of tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-DCP).
By using such a polymerizable compound, an organic layer can be formed with good adhesion on a support having a low retardation value such as a COP film.

JP 2013-49019 A International Publication No. 2014/027521 JP 2014-172231 A

In general, the organic layer is prepared by preparing a composition containing a compound to be the organic layer, and applying and drying the composition on the surface of the support, and then applying the compound by ultraviolet irradiation or the like as necessary. It is formed by a coating method that cures.
However, according to the study of the present inventor, the coating film made of the composition containing the polymerizable compound described in Patent Document 3 may not have sufficient viscosity in the reduced-rate dry state. If the viscosity in the reduced-rate dry state is insufficient, for example, foreign matter attached to the support tends to cause so-called repellency or the like in the coating film, and the organic layer that forms the inorganic layer on the entire surface of the support May not be formed properly.

Such a problem hardly occurs when an organic layer is formed in a relatively small area, such as a batch method.
However, when an organic layer is formed in a large area such as a so-called roll-to-roll, it is obstructed by foreign matter adhering to the support, the behavior of the composition when applied, the behavior of the composition when dried In addition, since the progress of ultraviolet curing has a great influence on the coating film and the organic layer to be formed, defects in the organic layer due to repelling and the like are likely to occur.

  In addition, the polymerizable compound described in Patent Document 3 has a low glass transition temperature, and depending on the formation conditions of the inorganic layer, the organic layer is etched by the plasma when forming the inorganic layer, and the inorganic layer is appropriate. A portion that cannot be deposited easily occurs.

Furthermore, as described above, the support made of COP or the like may be deformed by the heat of plasma when forming the inorganic layer.
Considering this point, before forming the inorganic layer, an organic layer made of a (meth) acrylate polymer or the like having a high glass transition temperature is also formed, and this is caused by the heat of plasma when forming the inorganic layer. It is preferable to support the support with an organic layer against deformation.

  Therefore, the emergence of an organic / inorganic laminated gas barrier film having an organic layer using a (meth) acrylate polymer with high adhesion and high glass transition temperature on a support having a low retardation value such as a COP film or a COC film. It is desired.

  An object of the present invention is to solve such problems of the prior art. In an organic / inorganic laminated gas barrier film, a support having a low retardation value such as a COP film or a COC film has a glass transition temperature. An object of the present invention is to provide a gas barrier film having an organic layer using a high (meth) acrylate polymer with high adhesion, high gas barrier properties, and good transparency.

In order to achieve such an object, the gas barrier film of the present invention comprises a support having a retardation value of 20 nm or less, a primer layer formed on one surface of the support, and a surface on which the primer layer of the support is formed. One or more combinations of an inorganic layer and an organic layer that is the base of the inorganic layer formed on the side, and
The support has a value of a ^* in the L ^* a ^* b ^* color system of −0.3 to 0 and a value of b ^* of less than 0.5, or both satisfy, or the value of a ^* is − 1 to 0.5, and the value of b ^* satisfies 0.5 or more and less than 1.5,
The organic layer is a (meth) acrylic polymer layer, the organic layer is formed on the surface of the primer layer, and the primer layer has an acrylic polymer as a main chain, a side chain, and a terminal urethane resin having a polycarbonate group. The present invention provides a gas barrier film comprising a graft copolymer having at least one of polycarbonate-based urethane oligomers.

In such a gas barrier film of the present invention, the support is preferably a cycloolefin polymer or a cycloolefin copolymer.
Moreover, it is preferable that an organic layer is a polymer of the (meth) acryl compound more than trifunctional, and a glass transition temperature is 220 degreeC or more.
The graft copolymer preferably has a weight average molecular weight of 30,000 or more, and the primer layer preferably has a glass transition temperature of 50 ° C. or more.
In addition, on the surface of the support on the side on which the organic layer and the inorganic layer are formed, it is preferable that the layer farthest from the support is an organic layer having a thickness of 0.5 to 5 μm.
Moreover, it is preferable that the thickness of a primer layer is 0.01-0.3 micrometer.
Moreover, it is preferable that the glass transition temperature of a support body is lower than the glass transition temperature of an organic layer, and is 120 degreeC or more.
Furthermore, it is preferable that a ^* and b ^* in the L ^* a ^* b ^* color system are −2 to 2.

  In the gas barrier film of the present invention, the gas barrier film of the present invention is a support having a low retardation value such as a COP film or a COC film, and a (meth) acrylate polymer layer having a high glass transition temperature as an organic layer. It is a gas barrier film having high adhesion, high gas barrier properties, and good transparency.

It is a figure which shows notionally an example of the gas barrier film of this invention. It is a figure which shows notionally another example of the gas barrier film of this invention.

  Hereinafter, the gas barrier film of the present invention will be described in detail based on a preferred embodiment shown in the accompanying drawings.

In FIG. 1, an example of the gas barrier film of this invention is shown notionally.
A gas barrier film 10 shown in FIG. 1 basically includes a support 12, a primer layer 14 formed on one surface of the support 12, and an organic layer 16 formed on (on the surface of) the primer layer 14. And an inorganic layer 18 formed on the organic layer 16 on the primer layer 14 and an outermost organic layer 16 formed on the inorganic layer 18.
In the gas barrier film 10 shown in FIG. 1, the outermost surface, that is, the organic layer 16 that is the most separated from the support 12 is provided as a preferred embodiment.

As described above, the gas barrier film 10 shown in FIG. 1 includes an organic layer 16, an inorganic layer 18 formed on the organic layer 16, and an outermost organic layer 16 formed on the inorganic layer 18. Have That is, this gas barrier film 10 has one set of a combination of the organic layer 16 and the inorganic layer 18 that are the base.
However, in addition to this, the gas barrier film of the present invention can use various layer configurations.

For example, like the gas barrier film 20 shown in FIG. 2, the structure which has 2 sets of combinations of the organic layer 16 used as a foundation | substrate and the inorganic layer 18, and also has the organic layer 16 in the outermost surface may be sufficient. Or the structure which has three or more combinations of the organic layer 16 and the inorganic layer 18, and has the organic layer 16 on the outermost surface may be sufficient. The outermost organic layer is provided as a preferred embodiment as described above.
That is, the gas barrier film of the present invention has a primer layer 14 on the surface of the support 12 and further has an organic layer 16 on the primer layer 14 (surface) as an underlayer of the inorganic layer 18. Various organic-inorganic laminated structures having one or more combinations of an inorganic layer and an organic layer serving as a base for the inorganic layer can be used.
Here, as the number of combinations of the inorganic layer and the base organic layer, that is, the number of alternating layers of the organic layer and the inorganic layer increases, the gas barrier film becomes thicker, but a high gas barrier property is obtained.

In the gas barrier film 10, the support 12 is a transparent sheet having a retardation value (Reetardation (Re value)) of 20 nm or less.
The gas barrier film 10 of the present invention is used for applications requiring high optical characteristics such as sealing of an organic EL element by using the support 12 having a retardation value of 20 nm or less, preferably 10 nm or less. Has realized a good gas barrier film.

If the support 12 is transparent with a retardation value of 20 nm or less, various known sheet-like materials can be used.
Specifically, a resin film having a retardation value of 20 nm or less, made of a resin material such as polycarbonate (PC), cycloolefin polymer (COP), cycloolefin copolymer (COC), triacetyl cellulose (TAC), transparent polyimide, Preferably exemplified.
Among them, the COP film and the COC film are preferable in that the retardation value of the support 12 can be lowered, the moisture content is small, the inorganic layer 18 described later can be suitably formed, and the gas barrier property of the support 12 itself can be increased. The COP film is more preferably exemplified. Among them, the melt-type COP film is particularly preferably exemplified in that the cloudiness of the support 12 when forming the primer layer 14 can be surely prevented.

What is necessary is just to set the thickness of the support body 12 suitably according to a use, a forming material, etc.
According to the study of the present inventor, the thickness of the support 12 is preferably 5 to 100 μm, and more preferably 10 to 50 μm.
By setting the thickness of the support 12 in the above range, it is preferable in terms of ensuring sufficient mechanical strength of the gas barrier film 10, reducing the weight of the gas barrier film 10, reducing the thickness, and ensuring flexibility.

The support 12 preferably has a glass transition temperature (Tg) lower than that of the organic layer 16 and 120 ° C. or higher.
The support 12 having a retardation value of 20 nm or less, in particular, the support 12 made of COP or COC is often a crystalline polymer, and the glass transition temperature and the melting point are approximately equal. The organic layer 16 is a (meth) acrylic polymer layer.
Therefore, by making the glass transition temperature of the support 12 lower than that of the organic layer 16, the moldability as a resin film can be improved and the cost of the support 12 can be reduced. In addition, since the brittleness of the support 12 can be improved by making the glass transition temperature of the support 12 lower than that of the organic layer 16, for example, when carrying out roll-to-roll manufacturing, the transportability and the like are good. Thus, stable production becomes possible.
In addition, by setting the glass transition temperature of the support 12 to 120 ° C. or higher, sufficient heat resistance is achieved not only for heat due to drying when forming the organic layer 16 but also for heat such as plasma when forming the inorganic layer 18. Therefore, it is possible to suitably form the organic layer 16 having a high glass transition temperature and the high-density inorganic layer 18.
Considering such points, the glass transition temperature of the support 12 is preferably 140 ° C. or higher.

In the present invention, the glass transition temperature of the support 12 or each layer may be measured according to JIS K 7121 by differential scanning calorimetry.
The glass transition temperature may be a numerical value described in a catalog or the like.

In the gas barrier film 10, a primer layer 14 is formed on one surface of the support 12, and an organic layer 16 is formed on the surface of the primer layer 14.
The primer layer 14 is for bringing the support 12 and the organic layer 16 underlying the inorganic layer 18 into close contact with a sufficient adhesion. The primer layer 14 will be described in detail later.

  As described above, the gas barrier film 10 includes the organic layer 16 formed on the primer layer 14, the inorganic layer 18 formed on the organic layer 16, and the outermost surface formed on the inorganic layer 18. And an organic layer 16.

The organic layer 16 formed on the primer layer 14, that is, the organic layer 16 below the inorganic layer 18, is an underlayer for properly forming the inorganic layer 18 that mainly exhibits gas barrier properties in the gas barrier film 10. Function as.
By having the organic layer 16 as the base of such an inorganic layer 18, the surface of the support 12 is embedded and foreign matter adhering to the surface of the support 12 is embedded to form the inorganic layer 18. The film surface can be in a state suitable for forming the inorganic layer 18. As a result, there are no portions where the inorganic compound that becomes the inorganic layer 18 is difficult to deposit, such as irregularities on the surface of the support 12 or shadows of foreign matter, and there is no gap on the entire surface of the organic layer 16 so that there is no gap. 18 can be formed.

On the other hand, the outermost organic layer 16 is an organic layer that acts as a protective layer for the inorganic layer 18 and is provided as a preferred embodiment.
As described above, in the gas barrier film 10, it is the inorganic layer 18 that mainly exhibits gas barrier properties. Therefore, if the inorganic layer 18 is cracked or damaged, the gas barrier performance is reduced. On the other hand, by having the organic layer 16 as the protective layer on the outermost surface, it is possible to prevent the inorganic layer 18 from being damaged and develop the desired gas barrier performance over a long period of time.

The organic layer 16 is a layer made of an organic compound, and is obtained by polymerizing (crosslinking) monomers and oligomers that become the organic layer 16.
In the present invention, the organic layer 16 is a (meth) acrylic polymer layer, that is, an acrylic polymer or a methacrylic polymer whose main component is an acrylate and / or methacrylate monomer or oligomer polymer.
Among these, dipropylene glycol di (meth) acrylate (DPGDA), trimethylolpropane tri (meth) acrylate (TMPTA), dipenta, etc., particularly in terms of high glass transition temperature, high resistance to plasma, and high heat resistance. An organic layer 16 composed of an acrylic polymer or a methacrylic polymer, which is mainly composed of a polymer of a acrylate and / or methacrylate acrylate and / or methacrylate, such as erythritol hexa (meth) acrylate (DPHA), and more particularly trifunctional or higher, Preferably exemplified. It is also preferable to use a plurality of these acrylic polymers and methacrylic polymers.

In the present invention, the organic layer 16 is formed of such a (meth) acrylic polymer, so that it has a high glass transition temperature, high heat resistance and plasma etching resistance, and has a low refractive index and high transparency. The organic layer 16 having excellent characteristics is formed.
Therefore, the gas barrier film 10 of the present invention can suitably suppress the etching of the organic layer 16 due to plasma when forming the inorganic layer 18, and forms a proper inorganic layer 18 without omission on the entire surface of the organic layer 16. Is possible. As a result, the gas barrier film 10 exhibits a very high gas barrier property.
Furthermore, in the gas barrier film 10 of the present invention, the support 12 is supported by the organic layer 16 having a high glass transition temperature and excellent heat resistance. Therefore, the support 12 may be deformed by the heat of plasma when the inorganic layer 18 is formed. Can be prevented.

For the outermost organic layer 16 serving as a protective layer, a (meth) acrylic polymer obtained by polymerizing an ultraviolet curable urethane acrylic polymer can also be suitably used.
Specifically, this graft copolymer is polymerized using a graft copolymer having an acrylic polymer as a main chain and a side chain having a urethane polymer having an acryloyl group at the end and / or a urethane oligomer having an acryloyl group at the end. The (meth) acrylic polymer is preferably exemplified. This graft copolymer is highly transparent and hardly yellows.

The acrylic main chain in the graft copolymer may be formed by individually polymerizing (meth) acrylate monomer, ethyl acrylate monomer, etc., and any of these copolymers or any of these and other It may be a copolymer with a monomer. For example, a copolymer obtained from (meth) acrylic acid ester and ethylene is also preferable.
The acrylic main chain and the urethane polymer unit or the urethane oligomer unit may be directly bonded, or may be bonded via another linking group. Examples of other linking groups include ethylene oxide groups, polyethylene oxide groups, propylene oxide groups, and polypropylene oxide groups. The graft copolymer may contain multiple types of side chains in which urethane polymer units or urethane oligomer units are bonded via different linking groups (including direct bonds).

The graft copolymer preferably has a weight average molecular weight of 10,000 to 3000000, more preferably 10,000 to 250,000, and particularly preferably 12,000 to 200,000.
Further, this graft copolymer preferably has a double bond equivalent (acryl equivalent) of 500 g / mol or more, more preferably 550 g / mol or more, and preferably 600 g / mol or more. . Furthermore, the double bond equivalent of the graft copolymer is more preferably 2000 g / mol or less.

In the present invention, the weight average molecular weight (Mw) of various polymers (resins / polymer materials) may be measured by gel permeation chromatography (GPC) as a molecular weight in terms of polystyrene (PS). More specifically, the weight average molecular weight is HLC-8220 (manufactured by Tosoh Corporation), TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6.0 mm ID × 15.0 cm) as a column, and 10 mmol / L as an eluent. What is necessary is just to obtain | require by using a lithium bromide NMP (N-methylpyrrolidinone) solution.
As the weight average molecular weight of the polymer or the like, a numerical value described in a catalog or the like may be used.
Moreover, what is necessary is just to measure a double bond equivalent by a well-known method.

As such a graft copolymer, for example, a commercially available product such as an ultraviolet curable urethane acrylic polymer (Acryt 8BR series) manufactured by Taisei Fine Chemical Co., Ltd. may be used.
A plurality of graft copolymers may be used in combination.

The thickness of the organic layer 16 may be appropriately set according to the material for forming the organic layer 16 and the support 12. According to the study of the present inventor, the thickness of the organic layer 16 is preferably 0.5 to 5 μm, and more preferably 1 to 3 μm.
By setting the thickness of the organic layer 16 to 0.5 μm or more, the surface of the organic layer 16, that is, the surface of the inorganic layer 18, is embedded by embedding irregularities on the surface of the support 12 and foreign matters attached to the surface of the support 12. The film formation surface can be flattened.
In addition, by setting the thickness of the organic layer 16 to 5 μm or less, it is possible to suitably suppress the occurrence of problems such as cracks in the organic layer 16 and curling of the gas barrier film 10 caused by the organic layer 16 being too thick. be able to.

The outermost organic layer 16 acting as a protective layer preferably has a thickness of 0.5 to 5 μm, more preferably 1 to 3 μm.
By setting the thickness of the outermost organic layer 16 to 0.5 μm or more, it is possible to improve the protection performance of the inorganic layer 18 and obtain the gas barrier film 10 that expresses the desired gas barrier property over a long period of time. . By setting the thickness of the organic layer 16 on the outermost surface to 5 μm or less, cracks in the organic layer 16 and curling of the gas barrier film 10 can be suppressed as described above.

  When having a plurality of organic layers 16, the thickness of each organic layer 16 may be the same or different from each other. Moreover, the forming material of each organic layer 16 may be the same or different.

In the gas barrier film 10 of the present invention, since the organic layer 16 is a (meth) acrylic polymer, the glass transition temperature is basically high. Here, the organic layer 16, particularly the organic layer 16 formed on at least the primer layer 14, preferably has a glass transition temperature of 220 ° C. or higher, more preferably 230 ° C. or higher.
By setting the glass transition temperature of the organic layer 16 to 220 ° C. or higher, the inorganic layer 18 can be formed by preventing the etching of the organic layer 16 by plasma when forming the inorganic layer 18 and forming the appropriate inorganic layer 18. This is preferable in that the deformation of the support 12 due to the heat of the plasma can be prevented.

The organic layer 16 may be formed (film formation) by a known method for forming a layer made of an organic compound according to the material for forming the organic layer 16.
As an example, the organic layer 16 includes an organic solvent, an organic compound (monomer, dimer, trimer, oligomer, polymer, etc.) to be the organic layer 16, a photopolymerization initiator, a surfactant, a silane coupling agent, a softening agent, and the like. What is necessary is just to form a coating composition, apply | coat and dry this coating composition to the formation surface of an organic layer, and also polymerize an organic compound by ultraviolet irradiation (crosslinking / curing), and what is necessary is just to form.
The organic layer 16 is preferably formed by so-called roll-to-roll (hereinafter also referred to as RtoR). In the following description, “roll to roll” is also referred to as “RtoR”.
As is well known, RtoR is a film formed by feeding a film-forming material from a material roll formed by winding a long film-forming material into a roll and transporting the film-forming material in the longitudinal direction. In this manufacturing method, a film-formed material is wound into a roll. By using RtoR, high productivity and production efficiency can be obtained.

The inorganic layer 18 is a layer made of an inorganic compound.
In the gas barrier film 10, the inorganic layer 18 mainly exhibits the target gas barrier property.

The material for forming the inorganic layer 18 is not limited, and various layers made of an inorganic compound that exhibits gas barrier properties can be used.
Specifically, metal oxides such as aluminum oxide, magnesium oxide, tantalum oxide, zirconium oxide, titanium oxide, and indium tin oxide (ITO); metal nitrides such as aluminum nitride; metal carbides such as aluminum carbide; silicon oxide, Silicon oxides such as silicon oxynitride, silicon oxycarbide and silicon oxynitride carbide; silicon nitrides such as silicon nitride and silicon nitride carbide; silicon carbides such as silicon carbide; hydrides thereof; mixtures of two or more of these; and Films made of inorganic compounds such as these hydrogen-containing materials are preferably exemplified. A mixture of two or more of these can also be used.
In particular, silicon nitride, silicon oxide, silicon oxynitride, aluminum oxide, and a mixture of two or more thereof are preferably used because they are highly transparent and can exhibit excellent gas barrier properties. Among these, silicon nitride is particularly suitable because it has high transparency in addition to excellent gas barrier properties.

The thickness of the inorganic layer 18 may be appropriately determined according to the forming material, so that the target gas barrier property can be exhibited. According to the study of the present inventor, the thickness of the inorganic layer 18 is preferably 10 to 200 nm, more preferably 15 to 100 nm, and particularly preferably 20 to 75 nm.
By setting the thickness of the inorganic layer 18 to 10 nm or more, the inorganic layer 18 that stably expresses sufficient gas barrier performance can be formed. In addition, the inorganic layer 18 is generally brittle, and if it is too thick, there is a possibility that cracks, cracks, peeling, etc. may occur. However, if the thickness of the inorganic layer 18 is 200 nm or less, cracks will occur. Can be prevented.

  In addition, when it has the some inorganic layer 18 like the gas barrier film 20 shown in FIG. 2, the thickness of each inorganic layer 18 may be the same or different. Moreover, the forming material of each inorganic layer 18 may be the same or different.

In the gas barrier film 10, the formation method of the inorganic layer 18 is not limited, and various known inorganic layer (inorganic film) formation methods can be used depending on the inorganic layer 18 to be formed.
Specifically, the inorganic layer 18 may be formed by a gas phase film forming method such as plasma CVD such as CCP-CVD or ICP-CVD, sputtering such as magnetron sputtering or reactive sputtering, or vacuum deposition.
The inorganic layer 18 is also preferably formed by RtoR.

As described above, the gas barrier film 10 has the primer layer 14 on one surface of the support 12, and the organic layer 16 is formed on the primer layer 14.
In the present invention, the primer layer 14 is formed by curing (crosslinking) a graft copolymer having an acrylic polymer as a main chain and a side chain having at least one of a urethane polymer having a polycarbonate group as a terminal and a urethane oligomer having a polycarbonate group as a terminal. It is a thing.

  The gas barrier film 10 of the present invention has a primer layer 14 made of such a graft copolymer on the surface of a support 12, and an organic layer 16 made of a (meth) acrylate polymer on the primer layer 14. By using the support 12 having an excellent optical characteristic with a retardation value of 20 nm or less and having an organic layer 16 made of a (meth) acrylate polymer having a high glass transition temperature, the organic layer 16 (organic-inorganic The gas barrier film 10 having high adhesion between the laminated structure) and the support 12, high gas barrier properties, and good transparency is realized.

As described above, high optical properties are required for gas barrier films used for organic EL elements, solar cells, and the like. Therefore, in the gas barrier film corresponding to these uses, a support having a low retardation value such as a COP film is used.
As a gas barrier film having high gas barrier properties, an organic / inorganic laminated type gas barrier film having a combination of an inorganic layer and an organic layer serving as a base of the inorganic layer is known. Here, in the organic-inorganic laminated type gas barrier film, the glass transition temperature is high, the etching by plasma when forming the inorganic layer can be prevented, and a more appropriate inorganic layer can be formed. It is preferable to form the organic layer with a (meth) acrylate polymer in that the support can be prevented from being deformed by the heat of plasma during the formation, and the optical properties are excellent. In particular, in order to prevent the deformation of the support due to the heat of plasma when forming the inorganic layer, it is preferable to form an organic layer made of a (meth) acrylate polymer on the surface of the support.

However, a material having a low retardation value such as COP has a low polarity and therefore has very low adhesion to a (meth) acrylate polymer.
Therefore, when a laminated structure of an organic layer using an (meth) acrylate polymer as an organic layer and an inorganic layer is formed on a support made of COP, the organic layer is easily peeled off.

As a method for improving the adhesion, a method using a primer is exemplified. As a primer for improving the adhesion of the COP film, a urethane compound is generally used. Moreover, the polymerizable compound containing the condensed polycyclic hydrocarbon structure described in Patent Document 3 can also be used as a primer for improving the adhesion of the COP film.
However, according to the study of the present inventors, there are various problems even if the adhesion between the support made of COP film or the like and the organic layer made of (meth) acrylate polymer is improved by using these primers. Arise.

As is well known, when COP and COC are irradiated with ultraviolet rays, so-called yellowing occurs in which a yellowish tint is exhibited according to the amount of ultraviolet irradiation.
However, the organic layer made of a (meth) acrylate polymer is formed by polymerizing a (meth) acrylate monomer by irradiating ultraviolet rays. The ultraviolet rays at this time are also irradiated to the support. For this reason, the support made of COP or the like is yellowed by the irradiation of the ultraviolet rays.
As described above, the higher the number of combinations of the base organic layer and the inorganic layer, the higher the gas barrier property. However, as the number of formations of the organic layer increases, the amount of ultraviolet irradiation for forming the organic layer increases, and the yellowing of the support increases.
Such yellowing of the support is a serious problem in a gas barrier film that requires excellent optical characteristics, such as a gas barrier film for sealing the organic EL element described above.

Further, urethane-based primers and polymers of polymerizable compounds described in Patent Document 3 have a low glass transition temperature.
As described above, the organic layer is usually formed by a coating method. When forming an organic layer by a coating method, it is inevitable that a primer serving as a base is mixed into a coating composition for forming the organic layer.
However, when such a low glass transition temperature is mixed in the (meth) acrylic polymer forming the organic layer, the glass transition temperature of the organic layer is lowered. As a result, similar to the case where the organic layer is formed of a material having low glass transition temperature or plasma resistance, such as etching caused by plasma when forming the inorganic layer, or deformation of the support due to the heat of the plasma when forming the inorganic layer. Problem arises.

Furthermore, the urethane-based primer and the polymerizable compound described in Patent Document 3 have a small molecular weight, and the viscosity of the coating composition forming the organic layer is low.
Therefore, this coating composition has insufficient viscosity in the reduced-rate dry state, for example, a so-called repellency or the like is generated in the coating film due to foreign matters attached to the support, and the inorganic layer is formed on the entire surface of the support. It is not possible to properly form an organic layer that forms the surface of the film. As described above, this problem is conspicuous when an organic layer is formed in a large area such as RtoR.

On the other hand, in the present invention, a graft copolymer having an acrylic polymer as the main chain on the surface of the support 12 and a urethane polymer having a polycarbonate group at the end and / or a urethane oligomer having a polycarbonate group at the end as the side chain. The primer layer 14 is formed by curing and an organic layer 16 is formed on the primer layer 14.
In the following description, a graft copolymer having an acrylic polymer as a main chain and a side chain with a urethane polymer having a polycarbonate group at the end and / or a urethane oligomer having a polycarbonate group at the end is referred to as a “urethane acrylic copolymer”. Also say.

Therefore, in the gas barrier film 10 of the present invention, the adhesion between the support 12 and the organic layer 16 can be made extremely high by the action of the urethane polymer and / or the urethane oligomer that the primer layer 14 has.
In addition, since the urethane acrylic copolymer has a structure in which the acrylic polymer main chain has a side chain of urethane polymer and / or urethane oligomer, it is compared with a (meth) acrylate monomer that becomes the organic layer 16 when cured. As a result, a very large network structure is formed. Therefore, when the organic layer 16 is formed, (meth) acrylate monomer or the like enters this network structure, and the anchoring effect caused by this can also improve the adhesion between the support 12 and the organic layer 16.

The urethane acrylic copolymer has a polycarbonate having high resistance to ultraviolet rays at the ends of the urethane polymer and the urethane oligomer.
Therefore, as will be shown later in Examples, the gas barrier film 10 of the present invention can prevent yellowing of the support 12 by the action of this polycarbonate even when irradiated with ultraviolet rays to form the organic layer 16, and as a result. The gas barrier film 10 having excellent transparency and excellent optical properties can be obtained.

Further, since the urethane acrylic copolymer has an acrylic polymer main chain, it has a higher glass transition temperature after being cured than a urethane-based primer or the like.
Therefore, when the organic layer 16 is formed, even if a graft copolymer is mixed into the coating composition, the glass transition temperature of the organic layer 16 does not decrease. Thereby, the gas barrier film 10 of the present invention has an effect of having the organic layer 16 made of (meth) acrylic polymer, such as prevention of etching of the organic layer 16 and prevention of deformation of the support 12 when forming the inorganic layer 18. High gas barrier properties are expressed by making the best use of.
Furthermore, since the urethane acrylic copolymer is thermosetting, even if it is mixed in the coating composition forming the organic layer 16, curing of the organic layer 16 by ultraviolet rays is not hindered.

The urethane acrylic copolymer is a copolymer of an acrylic polymer, a urethane polymer and / or a urethane oligomer, and a polycarbonate, and therefore has a very large molecular weight as compared with a urethane-based primer or the like.
Therefore, the coating composition for forming the primer layer 14 containing the urethane acrylic copolymer has a high viscosity in a reduced-rate dry state, and does not cause repelling of the coating film due to foreign matters attached to the support, The organic layer 16 serving as the formation surface of the inorganic layer 18 can be appropriately formed on the entire surface of the support 12, and the primer layer 14 itself can be thinned. Moreover, since the repellency etc. of a coating film can be prevented, it can respond suitably also to formation of the primer layer 14 by RtoR.
Therefore, since the gas barrier film 10 of the present invention can form the inorganic layer 18 on the appropriate organic layer 16, this also exhibits high gas barrier properties.

Moreover, since the cured product of the urethane acrylic copolymer has good coatability with respect to an organic solvent or the like, the coatability of the coating composition for forming the organic layer 16 is also good. Also in this respect, the proper organic layer 16 is formed. it can.
In addition, an appropriate organic layer 16 can be formed, and the primer layer 14 itself also has high heat resistance at a high glass transition temperature. Therefore, the organic layer 16 can be thinned, and as a result, the gas barrier film 10 is thinned. be able to.

Further, the primer layer 14 obtained by curing the urethane acrylic copolymer is formed by a coating method. Here, the urethane acrylic copolymer is a coating composition that forms the organic layer 16 after the coating composition is dried and solidified to some extent, becomes a so-called tack-free state, and becomes tack-free. May be applied.
Therefore, unlike the case where a urethane-based primer is used, there is no need to perform a sequential multi-layering process in which the primer and the coating composition for forming the organic layer 16 are continuously applied. That is, in the case of RtoR, after the primer layer 14 is formed, the organic layer 16 can be formed by winding it once to form a roll, and then feeding the support from the roll.

  As described above, in the present invention, the urethane acrylic copolymer forming the primer layer 14 has an acrylic polymer as a main chain, a side chain with a urethane polymer having a polycarbonate group at the end and / or a urethane oligomer having a polycarbonate group at the end. A urethane-modified acrylic graft copolymer (urethane-modified acrylic polymer).

  The urethane acrylic copolymer may be a copolymer having a structure in which urethane monomer units having a terminal polycarbonate group are arranged as side chains at the monomer units of the acrylic main chain serving as a trunk. What is necessary is just to have the structure formed by copolymerization.

The acrylic main chain in the urethane acrylic copolymer may be formed by individually polymerizing an acrylate monomer, an ethyl acrylate monomer, etc., and any of these copolymers or any of these and other monomers Copolymers of For example, a copolymer obtained from (meth) acrylic acid ester and ethylene is also preferable.
The side chain bonded to the acrylic main chain is a side chain containing a urethane polymer unit or a urethane oligomer unit. The graft copolymer may have a plurality of urethane polymer units having different molecular weights or urethane oligomer units having different molecular weights. The molecular weight of the urethane polymer unit may be, for example, 1000 to 10,000. Moreover, the molecular weight of a urethane oligomer unit should just be 100-1000, for example. The urethane acrylic copolymer may have both a side chain containing a urethane polymer unit and a side chain containing a urethane oligomer unit.

The urethane acrylic copolymer has a polycarbonate group at the end of the urethane side chain. The polycarbonate group is formed by polymerizing a monomer unit having a carbonate group.
One polycarbonate group may be composed of the same monomer unit or may be a copolymer composed of a plurality of different monomer units.
Moreover, the polycarbonate group of each urethane side chain may be the same or different in molecular weight and structure.

The urethane acrylic copolymer may have other side chains other than the side chain containing a urethane polymer unit or a urethane oligomer unit. Examples of other side chains include (meth) acryloyl groups and linear or branched alkyl groups. The linear or branched alkyl group is preferably a linear alkyl group having 1 to 6 carbon atoms, more preferably an n-propyl group, an ethyl group, or a methyl group, and even more preferably a methyl group.
The urethane acrylic copolymer may have a structure including a plurality of types of side chains that differ in the molecular weight of the urethane polymer unit or the urethane oligomer unit or a linking group, and a plurality of the other side chains described above.

The urethane acrylic copolymer that forms the primer layer 14 preferably has a weight average molecular weight of 10,000 to 100,000, more preferably 20,000 to 60,000.
By setting the weight average molecular weight of the urethane acrylic copolymer within this range, the viscosity of the coating composition for forming the primer layer 14 in the reduced drying state is made appropriate, and the primer layer 14 is formed on the entire surface of the support 12 without any gaps. High molecular weight that can be formed, can be tack-free without depending on the strength of the degree of cure, and can have good curability. Even when mixed with the underlying organic layer 16, the specific gravity is heavy, making it difficult to appear on the surface layer. This is preferable in that it does not cause defects. Tack-free means that there is no occurrence of blocking or sticking in a wound state.

In the present invention, the primer layer 14 preferably has a glass transition temperature of 20 ° C. or higher, more preferably 50 ° C. or higher.
By setting the glass transition temperature of the primer layer 14 to 20 ° C. or higher, the glass transition temperature of the organic layer 16 formed on the primer layer 14 can be kept high, and the organic layer 16 in forming the inorganic layer 18 can be maintained. This is preferable in that etching and deformation of the support 12 can be prevented.

As such a urethane acrylic copolymer, a commercially available product such as an Acryt 8UA series polycarbonate such as Acryt 8UA-347H or Acryt 8UA-540H, which is a urethane-modified acrylic polymer manufactured by Taisei Fine Chemical Co., Ltd. may be used.
A plurality of urethane acrylic copolymers may be used in combination.

What is necessary is just to set the thickness of the primer layer 14 suitably according to the forming material etc. of the primer layer 14, and the thickness which can obtain the target adhesive improvement effect.
According to the study of the present inventors, the thickness of the primer layer 14 is preferably 0.01 to 0.3 μm, more preferably 0.03 to 0.15 μm.
By setting the thickness of the primer layer 14 to 0.01 μm or more, the effect of having the primer layer 14 is reliably expressed, and the adhesion between the support 12 and the organic layer 16 can be sufficiently increased. Is preferable.
In addition, by setting the thickness of the primer layer 14 to 0.3 μm or less, it is possible to prevent the gas barrier film 10 from being thickened due to the primer layer 14 becoming unnecessarily thick. 16 is preferable in that mixing with 16 can be reduced.

Such a primer layer 14 may be formed by a known coating method.
That is, a coating composition prepared by dissolving or dispersing the above urethane acrylic copolymer in an organic solvent or the like is prepared, and the prepared coating composition is applied to the surface of the support 12 and dried by heating or the like. Furthermore, the primer layer 14 may be formed by curing by heating as necessary.
In addition, you may add a thermal-polymerization initiator, surfactant, a dispersing agent, etc. to the coating composition containing a urethane acrylic copolymer as needed.
Moreover, it is preferable to form such a primer layer 14 by RtoR.

Thus, after forming the primer layer 14 on the surface of the support 12, the organic layer 16 is formed on the primer layer 14 as described above, and the inorganic layer is formed on the organic layer 16 as described above. 18 is formed, and the outermost organic layer 16 is formed on the inorganic layer 18 as described above to manufacture the gas barrier film 10 of the present invention.
In addition, like the gas barrier film 20 shown in FIG. 2, the production of the gas barrier film having two or more combinations of the organic layer 16 and the inorganic layer 18 serving as a base depends on the number of combinations of the organic layer and the inorganic layer. Thus, the alternate formation of the organic layer 16 and the inorganic layer 18 may be repeated.

Gas barrier film 10 of the present invention, the a ^* in the L ^* a ^* b ^* color system is preferably from -2 to 2, and more preferably -1.5～1.5. The gas barrier film 10 of the present ^{invention, L * a * b * b} * is in the color system is preferably from -2 to 2, and more preferably -1.5～1.5.
As described above, the gas barrier film 10 of the present invention is a highly transparent film that prevents yellowing of the support 12 of the organic layer 16, and thus has excellent transparency and good optical properties. A gas barrier film 10 is obtained.
In addition, what is necessary is just to measure a ^* and b ^* of the gas barrier film 10 based on JISZ8781-4 using a haze meter etc.

  As described above, the gas barrier film of the present invention has been described in detail, but the present invention is not limited to the above examples, and various improvements and modifications may be made without departing from the scope of the present invention. Of course.

Hereinafter, the present invention will be described in more detail with reference to specific examples of the present invention.
[Example 1]
<Support 12>
A COP film (manufactured by JSR, Arton film, Tg = 150 ° C.) having a width of 1000 mm, a thickness of 80 μm, and a length of 100 m was used as the support 12.

<Formation of primer layer 14>
For diluting the above-mentioned urethane acrylic copolymer (manufactured by Taisei Fine Chemical Co., Ltd., ACRYT 8UA347H, weight average molecular weight 40000) with methyl ethyl ketone (MEK) so as to have a solid content concentration of 3% by mass to form the primer layer 14 A coating composition was prepared.
The prepared coating composition was filled into a predetermined position of a coating unit of a general RtoR film forming apparatus having a coating unit by a die coater and a drying zone by heating. Further, the roll around which the support 12 was wound was loaded into a predetermined position of the film forming apparatus and inserted through a predetermined transport path.
In the film forming apparatus, while the support 12 was conveyed in the longitudinal direction, the coating composition was applied to the support 12 by a die coater, and the primer layer 14 was formed by passing through a drying zone at 80 ° C. for 3 minutes. Then, after sticking the protective film made from PE on the surface of the primer layer 14, it wound up, and it was set as the roll which formed the primer layer 14 on the support body 12. FIG.
The coating amount of the coating composition was 3.5 mL (liter) / m ² . The formed primer layer had a thickness of 0.1 μm.
It was 54 degreeC when the glass transition temperature of the formed primer layer 14 was measured based on JISK7121 by the differential scanning calorimetry.

<Formation of organic layer 16>
TMPTA (manufactured by Daicel Cytec Co., Ltd.) and a photopolymerization initiator (manufactured by Lamberti Co., ESACURE KTO46) are prepared and weighed so that the mass ratio is 95: 5, so that the solid content concentration is 15% by mass. A coating composition for forming the organic layer 16 was prepared by dissolving in MEK.
A coating composition for forming the organic layer 16 is filled in a predetermined position of a coating unit of a general RtoR film forming apparatus having a coating unit by a die coater, a drying zone by hot air, and a curing zone by ultraviolet irradiation. did. Further, a roll formed by winding the support 12 on which the primer layer 14 was formed was loaded at a predetermined position of the film forming apparatus, and the support 12 was inserted into a predetermined transport path.
In the film forming apparatus, the protective film was peeled off while the support 12 was transported in the longitudinal direction, the coating composition was applied to the primer layer 14 by a die coater, and passed through a drying zone at 50 ° C. for 3 minutes. Thereafter, the coating layer was cured by irradiating with ultraviolet rays in the curing zone (accumulated dose of about 600 mJ / cm ² ) to form the organic layer 16. After sticking the PE protective film on the surface of the organic layer 16, the roll was wound up to form the organic layer 16. The thickness of the organic layer 16 was 1 μm.
It was 250 degreeC when the glass transition temperature of the formed organic layer 16 was measured similarly to the primer layer 14. FIG.

<Formation of inorganic layer 18>
The roll of the support 12 on which the organic layer 16 is formed is loaded into a predetermined position of a general CVD film forming apparatus for forming a film by CCP-CVD (capacitive coupling plasma CVD) using RtoR, and the support. 12 was inserted into a predetermined transport path.
In this CVD film forming apparatus, after the protective film is peeled off while transporting the support 12 on which the organic layer 16 is formed in the longitudinal direction, a silicon nitride film is formed as an inorganic layer 18 on the organic layer 16, A gas barrier film was prepared. Then, after sticking the protective film made from PE to the inorganic layer 18, it wound up.
That is, this gas barrier film has the same configuration as the gas barrier film 10 shown in FIG. 1 except that it does not have the outermost organic layer 16.
Silane gas (flow rate 160 sccm), ammonia gas (flow rate 370 sccm), hydrogen gas (flow rate 590 sccm), and nitrogen gas (flow rate 240 sccm) were used as source gases. The power supply was a high frequency power supply with a frequency of 13.56 MHz, and the plasma excitation power was 800 W. The film forming pressure was 40 Pa. The film thickness of the inorganic layer 18 was 50 nm.

[Example 2]
A gas barrier film was produced in the same manner as in Example 1 except that the support 12 was changed to a COC film (Gunze, F1 film, Tg = 180 ° C.) having a width of 1000 mm, a thickness of 100 μm, and a length of 100 m.

[Example 3]
Except that the support 12 was changed from the ARTON film to the same COP film, the width 1000 mm, the thickness 80 μm, and the length 100 m of an appel film (Zeon, Tg = 136 ° C.), the same as in Example 1. A gas barrier film was prepared.

[Example 4]
In preparation of the coating composition for forming the organic layer 16, TMPTA is blended with PET30 (Nippon Kayaku Co., Ltd., Kayarad) so that the mass ratio is 10: 2, and this blend and the polymerization initiator are massed. An organic layer 16 was formed in the same manner as in Example 1 except that the ratio was 95: 5, and a gas barrier film was produced.
It was 200 degreeC when the glass transition temperature of the organic layer 16 was measured similarly to Example 1. FIG.

[Example 5]
<Formation of outermost organic layer 16>
The above-mentioned graft copolymer forming the outermost organic layer 16 (manufactured by Taisei Fine Chemical Co., Ltd., Acryt 8BR-930, weight average molecular weight 16000, double bond equivalent 800), and photopolymerization initiator (manufactured by BASF, Irgacure 184) ), A silane coupling agent (manufactured by Shin-Etsu Silicone Co., Ltd., KBM5103) and a softening agent (manufactured by Toyobo Co., Ltd., Byron U1400) are weighed so that the mass ratio is 78: 10: 10: 2, and these are solid. It melt | dissolved in MEK so that a partial concentration might be 15 mass%, and the coating composition for forming the organic layer 16 of the outermost layer was prepared.

Coating composition for forming the outermost organic layer 16 at a predetermined position of a coating section of a general RtoR film forming apparatus having a coating section by a die coater, a drying zone by hot air, and a curing zone by ultraviolet irradiation. The product was filled. Further, a roll formed by winding the same gas barrier film as in Example 1 was loaded at a predetermined position of the film forming apparatus, and the gas barrier film was inserted into a predetermined transport path.
In the film forming apparatus, the protective film was peeled off while transporting the gas barrier film 10 in the longitudinal direction, the coating composition was applied to the inorganic layer 18 with a die coater, and passed through a drying zone at 100 ° C. for 3 minutes. Thereafter, the coating composition is cured by irradiating ultraviolet rays in the curing zone (accumulated dose of about 600 mJ / cm ² ) to form the outermost organic layer 16, thereby producing a gas barrier film 10 as shown in FIG. And wound into a roll.

[Example 6]
In the formation of the primer layer 14, a gas barrier film was produced in the same manner as in Example 1 except that the coating amount of the coating composition by the die coater was changed.
The thickness of the formed primer layer 14 was 0.01 μm.

[Example 7]
In the formation of the primer layer 14, a gas barrier film was produced in the same manner as in Example 1 except that the coating amount of the coating composition by the die coater was changed.
The thickness of the formed primer layer 14 was 0.3 μm.

[Comparative Example 1]
A gas barrier film was produced in the same manner as in Example 1 except that the primer layer 14 was not formed on the surface of the support 12.

[Comparative Example 2]
A gas barrier film was produced in the same manner as in Example 1 except that the material for forming the primer layer was changed from Acryt 8UA347H to Acryt 8UA146 (weight average molecular weight 30000) manufactured by Taisei Fine Chemical Co., Ltd.
This acrylic 8UA146 has an acrylic polymer as the main chain and a urethane polymer and / or urethane oligomer as the side chain, as in the case of the acrylic 8UA247H used in Example 1, but the ends of the urethane polymer and urethane oligomer are the same. Polyester, not polycarbonate.
The formed primer layer had a thickness of 0.1 μm. Moreover, it was 50 degreeC when the glass transition temperature of the primer layer was measured similarly to Example 1. FIG.

[Comparative Example 3]
A gas barrier film was produced in the same manner as in Example 5 having the outermost organic layer 16 except that a primer layer was formed in the same manner as in Comparative Example 2.

[Comparative Example 4]
Tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-DCP) and a polymerization initiator (Lamberti Co., Ltd., ESACURE KTO46) were prepared and weighed so that the mass ratio was 93: 7. These were dissolved in a solvent containing 2-butanone and propylene glycol 1-monomethyl ether 2-acetate so that the solid content concentration was 3% by mass to prepare a coating composition for forming a primer layer.
A gas barrier film was produced in the same manner as in Example 1 except that a primer layer was formed using this coating composition. In the formation of the primer layer, the coating composition was cured with ultraviolet rays in a nitrogen atmosphere with an oxygen content of 100 ppm or less, and the cumulative irradiation amount of ultraviolet rays was about 700 mJ / cm ² .
The formed primer layer had a thickness of 0.1 μm. Moreover, it was 200 degreeC when the glass transition temperature of the primer layer was measured similarly to Example 1. FIG.

[Comparative Example 5]
Urethane polymer (manufactured by Taisei Fine Chemical Co., Ltd., ACRYT WBR2000U) and a curing agent (manufactured by Tosoh Corp., Coronate L) are prepared and weighed so that the mass ratio is 100: 17, and the solid content concentration is 3% by mass. A coating composition for forming a primer layer was prepared by dissolving in Izopurpyrualcohol so that
A gas barrier film was produced in the same manner as in Example 1 except that a primer layer was formed using this coating composition.
The formed primer layer had a thickness of 0.1 μm. Moreover, it was 40 degreeC when the glass transition temperature of the primer layer was measured similarly to Example 1. FIG.

[Evaluation]
About each produced gas barrier film, gas-barrier property, adhesiveness, and yellowing were evaluated.
<Gas barrier properties>
The water vapor permeability [g / (m ² · day)] of the produced gas barrier film was measured by a calcium corrosion method (a method described in JP-A-2005-283561). The conditions for the constant temperature and humidity treatment were a temperature of 40 ° C. and a humidity of 90% RH.
The evaluation is as follows.
A: Water vapor transmission rate is less than 5 × 10 ⁻⁵ [g / (m ² · day)] B: Water vapor transmission rate is 5 × 10 ⁻⁵ [g / (m ² · day)] or more, 1 × 10 ⁻⁴ Less than [g / (m ² · day)] C: Water vapor transmission rate is 1 × 10 ^-4 [g / (m ² · day)] or more and less than 5 × 10 ^-4 [g / (m ² · day)] D: Water vapor transmission rate is 5 × 10 ⁻⁴ [g / (m ² · day)] or more and less than 1 × 10 ⁻³ [g / (m ² · day)] E: Water vapor transmission rate is 1 × 10 ⁻³ [g / (m ²・ day)] or more

<Adhesion>
Evaluation was made by a cross-cut peel test in accordance with JIS K5400.
Using a cutter knife, 90 ° cuts were made at 1 mm intervals on the organic layer and inorganic layer forming surfaces of each gas barrier film to make 100 grids with 1 mm intervals. On top of this, the tape affixed with a 2 cm wide Mylar tape (manufactured by Nitto Denko, polyester tape, No. 31B) was peeled off. The organic layer 16 formed on the primer layer 14 was evaluated by the number of cells remaining.
The evaluation is as follows.
A: The number of remaining cells is 100 B: The number of remaining cells is 90 to 99 C: The number of remaining cells is 80 to 89 D: The number of remaining cells is 80 or less

<Yellowing>
The yellowing state was evaluated by measuring a ^* and b ^* in the L ^* a ^* b ^* color system using a spectroscopic haze meter SH7000 manufactured by Nippon Denshoku Co., Ltd.
The evaluation is as follows.
A: The value of a ^* is −0.3 to 0 and the value of b ^* is less than 0.5 and satisfies both. B: The value of a ^* is −0.5 to 0 and the value of b ^* C: a value of a ^* is −1 to 0.5, and a value of b ^* is 1 or more and less than 1.5. D: a ^* The value of -1.5 to 1 and the value of b ^* are not less than 1.5 and less than 2.5. E: The value of a ^* is outside the range of -1.5 to 1, and The following table shows the results that satisfy any of the values of b ^* of 2.5 or more.

As shown in Table 1, Examples 1 to 7, which are gas barrier films of the present invention, all have good gas barrier properties and adhesion of the organic layer 16, and are transparent with little yellowing of the support. It is a gas aria film with excellent properties. In particular, when the glass transition temperature of the base organic layer is 250 ° C., good gas barrier properties are exhibited by the effect of the base organic layer having a high glass transition temperature. In Example 7 in which the primer layer having a polycarbonate was thickened, the adhesion was slightly low, but yellowing was further suppressed by the effect of the primer.
On the other hand, Comparative Example 1 having no primer layer has insufficient gas barrier properties and adhesiveness, and yellowing is greatly generated.
In Comparative Examples 2 to 4, in which the primer layer is acrylic that does not contain polycarbonate, the gas barrier property and the adhesion of the organic layer 16 are good, but the yellowing of the support due to the irradiation of ultraviolet rays is strongly generated.
Further, in Comparative Example 5 in which the primer layer is a urethane-based material having no acrylic, peeling occurs between the primer and the underlying organic layer which is acrylic, and the yellowness of the support by ultraviolet irradiation is low. Strange changes are occurring.
From the above results, the effects of the present invention are clear.

  It can be suitably used for organic EL elements, solar cells, and the like.

10, 20 Gas barrier film 12 Support 14 Primer layer 16 Organic layer 18 Inorganic layer

Claims (8)

A support having a retardation value of 20 nm or less, a primer layer formed on one surface of the support, an inorganic layer formed on the surface of the support on which the primer layer is formed, and a base of the inorganic layer One or more combinations of organic layers to be
The support has both a value of a ^* in the L ^* a ^* b ^* color system of −0.3 to 0 and a value of b ^* of less than 0.5, or the value of a ^* is -1 to 0.5 , and the value of b ^* satisfies 0.5 or more and less than 1.5,
The organic layer is a (meth) acrylic polymer layer, the organic layer is formed on the surface of the primer layer, and the primer layer has an acrylic polymer as a main chain, a side chain, and a terminal having a polycarbonate group. A gas barrier film comprising a graft copolymer having at least one of a urethane polymer and a urethane oligomer having a terminal polycarbonate group.   The gas barrier film according to claim 1, wherein the support is a cycloolefin polymer or a cycloolefin copolymer.   The gas barrier film according to claim 1 or 2, wherein the organic layer is a polymer of a tri- or higher functional (meth) acrylic compound and has a glass transition temperature of 220 ° C or higher.   The gas barrier film according to any one of claims 1 to 3, wherein the graft copolymer has a weight average molecular weight of 30000 or more, and the primer layer has a glass transition temperature of 50 ° C or more.   5. The organic layer having a thickness of 0.5 to 5 μm is the most separated layer from the support on the surface of the support on the side where the organic layer and the inorganic layer are formed. 5. 2. The gas barrier film according to item 1.   The gas barrier film according to claim 1, wherein the primer layer has a thickness of 0.01 to 0.3 μm.   The gas barrier film according to any one of claims 1 to 6, wherein a glass transition temperature of the support is lower than a glass transition temperature of the organic layer and is 120 ° C or higher. The gas barrier film according to any one of claims 1 to 7, wherein a ^* and b ^* in the L ^* a ^* b ^* color system are -2 to 2.